DE2110971A1 - N, N, N ', N'-tetrabenzyl-4-4'- and its uses - Google Patents

Description

April 27, 1971 C-886

CALGON CORPORATION P.O.Box 1346, Pittsburg, Pa., V.St.A.

, Ν, Ν ¹ , N'-tetrabenzyl-4, Vo: xydianiline and its use

The invention relates to that represented by the formula

) - ^CH

-CH

Composition shown Ν, Ν, Ν ¹ , 1T ^I- tetrabenzyl-4,4 ^I -oxydianiline and its use as an organic photoconductor for the production of photoconductive layers.

The present invention is to electrographic fabrics, and more particularly to a novel organic photoconductor and its use in the production of photographic

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conductive elements for electrographic images. The present invention is particularly directed to the novel composition IT, II, IT ¹ , K'-tetrabenzyl-Λ, 4'-oxydianiline and its use as a photoconductor.

The term electrophotography, like it, means in general understood in the art, a reproducing or copying process in which a combination of the Phenomena of electrostatics and the photoconductivity of substances are used, - El ektrophot ο graphic processes, which depend on photoconductive layers are known in the art. The most widely used method are xerography, in which a drum coated with selenium is used as a phot-sliding element is made, and "Electrofax", in which zinc oxide is used as a photoconductor is used. However, there are many more photographic processes that rely on photoconductivity are based, known and described in the literature.

In a elektrophotographisehen method is the electrophotographic element consisting essentially of a layer of the photoconductive compound as a coating _c? .Uf a relatively more conductive carrier, such as electro-conductive paper, aluminum foil, and the like., Is applied. In use, the photoconductive layer is electrically charged in the dark by means of a corona discharge or the like, so that the coating has a uniform positive or negative charge on its surface. The element is then exposed to an image of light which activates the photoconductive compound and an invisible charge pattern is developed on the element. The invisible charge image is then developed in a manner known to the person skilled in the art by means of an electrostatically charged clay bath (“toner”).

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Much research has been done on it in recent years related to the development of suitable photoconductive Try fabrics. In the past "they were based most of the photoconductive layers used in electrophotographic processes are on top of them inorganic substances such as selenium, zinc oxide, cadmium sulfide and the like, as a photosensitive member. Much has been made but related to the study of organic photovoltaics.

Most notable among the organic photoconductors that have been used heretofore are anthracene, anthraquinone, carbazole and perylene. Recently a lot of research on the Vei'wendung of organic photoconductors, such as polyvinyl carbazole, N, R, Ii ^1, N ¹ -tetrasubstit.-p-phenylenediamine and the disubstituted Benzylidenazinen and the like, was. Used. For example, see U.S. Patent 3,421,891, which is directed to polyvinylcarbazole, and U.S. Patent 3 $ 14,788, which refers to the use of the Γί, ϊΤ, ϊί ', N ¹ -tetrasubstituted-p-phenylenediamines (I ¹ SPU) and U.S. Patent 3,290,147 directed to the use of the N-disubstituted benzylidenazines.

However, many of these organic photoconductors are different Disadvantages associated. For example, some of the compounds are not as photosensitive as desired. A another pig-bending disadvantage, especially the TSPD compounds are accompanied by their limited solubility. The solubility of these compounds in the systems preferred by the industry is very limited, and the compounds tend to crystallize out instead of forming a uniform coating. Hence it is an aim of the present Invention to provide a novel, organic, photoconductive compound used in the manufacture of photoconductive Elements is useful.

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ORIGINAL fNSPECTED

Cal & on Corporation · C-886 ^

It has been found that N, N, N ', N'-tetrabenzyl- ^ V-oxydi aniline

a good photoconductor connection is and during manufacture of photoconductive elements is very useful. The inventive, The novel photoconductor is compatible with most of the common resin binder systems that are used in the manufacture used by electrophotographic plates, compatible, In addition, the novel compound according to the invention is also in most of the common solvents that Preferred by industry, easily soluble.

It is not intended to affect the invention by any Theories are limited, but it is assumed that the ither functional group will limit the usefulness of the inventive Connection increased. First, the non-fraction electrons on the ether oxygen atom improve photoconductivity the compound according to the invention. Then changed the presence of ether oxygen also affects the solubility properties. Example; - / ei se is the one according to the invention The compound is soluble in solvents such as cyclohexanone and the like, while the TSPD-type compounds are not are so easily soluble .. The compound according to the invention therefore brings an improvement over the known State of the art connections with itself.

The N, N, N ¹ , IT-tetrabenzyl - ^^ '- oxydianiline according to the invention was prepared as follows:

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! MSPECTED

Calgon Corporation C-886

example 1

'Manufacture; of N, N, N ', N'-tetrabenzyl-4,4'-oxydiani lin

In a 1 liter four-necked flask with a mechanical Was equipped with a stirrer, a reflux condenser, a thermometer and a feed funnel, 0.2 mol of 4,4 -'-oxydianiline, dissolved in 300 ml of Fischer's alcohol reagent (ethanol denatured with methanol and isopropanol). Then 0.8 moles of benzyl chloride was added to the reaction flask and the mixture was brought to reflux temperature brought. Then 0.8 moles of potassium hydroxide dissolved in 150 ml of alcohol reagent was added over the course of half an hour added dropwise. After the potassium hydroxide addition was complete, the reaction mixture was refluxed for 1 hour cooked. The reaction mixture became hot in 1000 ml Poured water to dissolve the potassium chloride that had precipitated. The resulting mixture was filtered and the The precipitate was washed several times with hot water. Of the Precipitate was dissolved in chloroform and decolorized with activated Nuchar charcoal. The Tetrabenzyloxydianüin was crystallized from the chloroform solution by addition of alcohol reagent. As a result, N, N, N ', H'-tetrabenzyl-4,4'-oxydiani were obtained lin, the melting point of which is 114 to 118 ° C in 74% yield.

Example 2 Production of Ν, Ν, Ν ', N'-tetrabenzyl-4,4'-oxydianiline

The following reaction mixture was placed in a 1 l four-necked flask equipped with a mechanical stirrer, a reflux condenser and a thermometer; (a) 20 g (0.1 MqI) of purified 4,4'-oxydianiline} (b) 50.4 g. (0 _Λ 4 MqI) benzyl chloride} (c) 33.6 g (0.4 mol) sodium bicarbonate and (d) a solvent system, which consists of 3OO ml

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Calgon Corporation · C-386

Ethanol "and 100 ml of distilled water. The reaction mixture was brought to reflux temperature and refluxed for about 5 hours. The refluxing was stopped as soon as no more CO 2 evolved from the reaction mixture The reaction mixture was then cooled and the heavy, oily phase was dissolved in chloroform, filtered and treated with charcoal. The tetrabenzyloxydianiline was crystallized from the chloroform solution by adding an alcohol reagent. As a result, 4-5.4 g (80% yield) of N, N, IV , N'-tetrabenzyl-4,4'-roxydianiline, the melting point of which was 114 to 118 ° C. The product obtained in this procedure was considerably less colored and crystallized more easily than the product obtained in Example 1.

The novel photoconductor of the present invention was evaluated in the following manner. The tetrabenzyloxydianuine (TBODA) was formulated with a solvent and a binder and then applied as 11k to a sheet of aluminum foil. The I ¹ BODA-im was charged in the dark with a high voltage corona and the charge uptake was measured. The charged film was then exposed to an ultraviolet light source and the charge dissipation measured and recorded. The batch used consisted of 15 g of polystyrene resin (Kopper ¹ s KTPL-7), 5 g of TBODA and 100 g of chloroform. The insensitive, photoconductive batch was applied as a film to aluminum foil, air-dried and then adapted in the dark for 24 hours before evaluation. The charge acceptance value (CA,) was measured by placing an electrode on the charged film immediately after the corona was broken. The ultraviolet light source was turned on after the charge acceptance was measured. The best charge (RC) was measured by the voltage level 15 seconds after the ultraviolet source was activated. The light source used was a UV fluorescent apparatus with a peak power output at J66O Si. The results of this

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Experiments demonstrate that TEODA has photoconductive properties. The experiment described above was repeated using different coated photoconductors instead of the I ¹ BODA. The other photoconductors evaluated using this procedure were K, N, N ¹ , N'-tetrabenzyl-paraphenylenediamine (TBPDA) and zinc oxide. Comparison of the results, as shown in Table I, shows that TBODA is a good photoconductor.

Table 1 Connection charge consumption (volts) Residual charge (volts)

TBPDA 400 150

ZnO * 600 0

TBODA 4-00 200

"A commercially available" Electrofax "sheet with a sensitizer additive

In addition to the evaluation described above, the TEODA photoliter was evaluated by an actual electrophotographic printing method. The TBODA-Pbotoleiter was prepared in a Harzbindemittelsystera, d ".c 10 g of a polystyrene resin (Kopper, ¹ s KTPL-7)" 1Ό0 r. L of chloroform, and 5 g of TBODA photoconductor containing Jjtnm was prepared an electrophotographic plate by A conductive substrate was coated with a TBODA approach using a pull rod Hr. 40. The conductive substrate was a laminate of aluminum foil, polyethylene and paper (Thilmany Paper Co. ITr. 85600) The substrate was roughened with steel wool and washed with chloroform, the resulting electroconductive plate was conditioned in the dark for 24 hours before use, and printing was then carried out by taping the photoconductive plate to a grounded base and a positive one for 30 seconds

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Corona of 5.0 kV. Then there was an IRE picture test card as a transparent photograph was quickly placed on the loaded plate, and the plate was then left for 5 seconds long exposed to ultraviolet light from the fluorescent source. The latent, charged Image was then made by dusting the leaves with a mixture of Bruning developer (type D) and iron filings and Removal of excess iron and developer using developed by a magnet. The plate was then made permanent by placing it in a 105 ° C for about 90 seconds was brought to the hot oven. The goodness of the print was considered rated satisfactory. This evaluation was given subjectively, and special attention was paid to the contrast, the resolution and the cleanliness of the background given. There were two additional electrophotographic Plates manufactured and tested in the same way using the TBODA approach, which is achieved by incorporating 0.005 S of a sensitizer had been improved. The two sensitizers used were 1-chloroanthraquinone and 2-methylanthraquinone. The goodness of the sensitized with the The print obtained on the plates was rated as good. Both sensitized records provided co-productions, the good · contrast and good resolution and one had a very clean background. In addition, electrophotographic plates were made and in the same Perhaps using a sensitized TBPDA approach checked instead of the TBODA. A comparison of the reproductions clearly showed that TBODA was equal to or slightly superior to TBPDA.

The electrophotographic elements according to the invention consist of an electrically conductive support which carries a photoconductive layer. The photoconductive layer consists essentially of a suitable, highly dielectric film-forming resinous binder which contains at least about 10 wt.% TECDA. In addition, the photoconductive

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Layer optionally contain a sensitizer.

The TBODA connection according to the invention is also compatible with others clear, resinous, dielectric binders in addition to polystyrene compatible. You can rait together other natural or synthetic, polymeric binders such as polyvinyl chloride, polyvinyl acetate, polyvinyl ether, styrene-butadiene copolymers, Polyvinylidene chloride, polyamides, polyacrylates and methacrylates, phenol-formaldehyde resins, Paraffin, mineral waxes and the like can be used. In addition, the binder system can be optional, as would be known to those skilled in the art is common to contain a plasticizer. The plasticizer may end up improving film strength and firmness Capability of the photoconductive layer of the electrophotographic element be used.

The TBODA compound is also in such solvents as Chloroform, toluene, methyl ethyl ketone, acetone, cyclohexanone and tetrahydrofuran, easily soluble.

The sensitizer component used in the present invention may be either of the dye sensitizer type or the chemical sensitizer type or a combination of the two types. The chemical type sensitizer is simply a chemical compound that increases photosensitivity of the photoconductor increased. To explain the mechanism of chemical sensitization have already been put forward many different theories; Generally speaking, however, it has been shown that aromatic quinones and cyano compounds die.Lichtensenzen der Photoconductors raise. Some examples of these types of connections are tetracyanoethylene, tetracyanoquinone dimethane (TCNQ), Anthraquinone and the substituted anthraquinones, such as 2-methylanthraquinone, 1-chloranthraquinone, 1-mit ro-anthraquinone and the like. A dye type sensitizer is one

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Compound showing the sensitivity of the photconductive Connection by enlarging or shifting the wavelength range, to which the photoconductor is photosensitive, increased. Examples of dye sensitizers are crystal violet, methylene blue, bhodamin B, rose bengal and the like

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Claims (1)

1. Ιί, Ιϊ, ΙΪ ¹ , Iv " ^l -'i'ctrabenzyl-4,4'-oxydian ^ lin. 2. Improved, photoconductive layer containing a highly dielectric, resinous binder and a photoconductive compound, characterized in that .sie
as photoconductive compound 13, Π, N *, 11 '-Tetrabenzyl- Contains 4,4'-oxydianalin. P " 5 Improved photoconductive layer according to Claim 2,
characterized in that it also contains a sensitizer. 4 ·. Improved, electrophographic element, containing a phctoconductive layer, which acts as a coating
a conductive support is applied, characterized in that the element as a photoconductive compound of the photoconductive layer Ν, Ν, ΪΪ ¹ , Ii'-TetroDeiiiiyl- ^ ·, 4'- l · " ι-ζγ dianiline released. 5. Improved Electrophotographic Seeing Process
Reproduction, characterized in that Kan (a)
an electrographic element that contains a photoconductive layer coated over a conductive layer
Carrier is applied, charges, (b) the element exposes an image to an invisible charge pattern
to generate, and (c) the invisible charge pattern with an electrostatically charged Lhtv; ickler developed, characterized in that the photoconductive compound of the photoconductive layer is ü, Ii, IT ¹ , K'-tetrabenzyl-4,4'-oxydianalin. 1 > - 11 10 985 1/1934 BATH